CN112358290B - 一种铁氧体材料及其制备方法和用途 - Google Patents

一种铁氧体材料及其制备方法和用途 Download PDF

Info

Publication number
CN112358290B
CN112358290B CN202011211159.XA CN202011211159A CN112358290B CN 112358290 B CN112358290 B CN 112358290B CN 202011211159 A CN202011211159 A CN 202011211159A CN 112358290 B CN112358290 B CN 112358290B
Authority
CN
China
Prior art keywords
ferrite material
ball milling
temperature
sintering
drying
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011211159.XA
Other languages
English (en)
Other versions
CN112358290A (zh
Inventor
吕飞雨
王媛珍
张利康
徐毅
周新成
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hengdian Group DMEGC Magnetics Co Ltd
Original Assignee
Hengdian Group DMEGC Magnetics Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hengdian Group DMEGC Magnetics Co Ltd filed Critical Hengdian Group DMEGC Magnetics Co Ltd
Priority to CN202011211159.XA priority Critical patent/CN112358290B/zh
Priority to PCT/CN2021/075239 priority patent/WO2022095296A1/zh
Priority to EP21888001.1A priority patent/EP4119523A4/en
Publication of CN112358290A publication Critical patent/CN112358290A/zh
Application granted granted Critical
Publication of CN112358290B publication Critical patent/CN112358290B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
    • C04B35/2641—Compositions containing one or more ferrites of the group comprising rare earth metals and one or more ferrites of the group comprising alkali metals, alkaline earth metals or lead
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
    • C04B35/2675—Other ferrites containing rare earth metals, e.g. rare earth ferrite garnets
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/6261—Milling
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63416—Polyvinylalcohols [PVA]; Polyvinylacetates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/10—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
    • H01F1/342—Oxides
    • H01F1/344—Ferrites, e.g. having a cubic spinel structure (X2+O)(Y23+O3), e.g. magnetite Fe3O4
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
    • H01F1/342—Oxides
    • H01F1/344—Ferrites, e.g. having a cubic spinel structure (X2+O)(Y23+O3), e.g. magnetite Fe3O4
    • H01F1/346—[(TO4) 3] with T= Si, Al, Fe, Ga
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3258—Tungsten oxides, tungstates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/442—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/604—Pressing at temperatures other than sintering temperatures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/606—Drying
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/608—Green bodies or pre-forms with well-defined density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/661—Multi-step sintering
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • C04B2235/762—Cubic symmetry, e.g. beta-SiC
    • C04B2235/764—Garnet structure A3B2(CO4)3
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Power Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Magnetic Ceramics (AREA)
  • Soft Magnetic Materials (AREA)

Abstract

本发明提供了一种铁氧体材料及其制备方法和用途。所述铁氧体材料的化学式为Bi1.3Cax+2yY1.7‑x‑2yFe5‑x‑yZrxWyO12；所述x为0.3～0.4，所述y为0.01～1。所述制备方法包括以下步骤：(1)将铁氧体材料的原料进行混合，烧结，得到铁氧体材料的前驱体；(2)将步骤(1)所述的铁氧体材料的前驱体再次进行混合，烘干，成型，烧结，得到所述铁氧体材料。所述铁氧体材料中的Bi和Ca元素能够替代部分稀土Y元素，Zr、W元素能够替代部分Fe离子，利用它们的电磁特性和补偿点来获得合适的4πMs、ΔH和Tc等参数。同时对应的制备工艺稳定且可重复性好，适合大批量生产，大大降低了生产成本。

Description

一种铁氧体材料及其制备方法和用途
技术领域
本发明属于微波通信领域及磁性材料领域，涉及一种铁氧体材料及其制备方法和用途。
背景技术
随着微波技术的迅猛发展，系统对元器件小型化的要求越来越迫切，而铁氧体元器件的体积远高于其他元器件，因此其小型化、轻量化的任务尤为重要。人们以前对微波铁氧体的研究多集中在材料的微波磁损耗方面，而对介电常数研究得相对较少。近年来，器件设计者对高介电常数材料，不断提出要求，特别是小线宽、高介电常数材料。于是高介电常数的石榴石材料成为了微波铁氧体研究领域中的热点之一。
现有微波铁氧体的介电常数在12～16之间，在低频环形器隔离器设计时器件尺寸偏大，无法满足小型化、集成化的需求。若提高铁氧体的介电常数到25以上，可以把隔离器环形器的尺寸缩小25％以上，达到小型化、集成化的需求。
当前4πMs＝1850～1950Gs的微波铁氧体材料在5G基站环形器或隔离器的应用较为广泛。关于高介电常数的微波铁氧体材料及制造方法的专利文献已有一些。
CN107746269A公开了一种低损耗功率旋磁材料，包括以下重量份原料：Bi203的重量份数为15～20份、Y2O3的重量份数为22～26份、GeO2的重量份数为1～2.5份、CaCO3的重量份数为2～5份、Fe2O3的重量份数为41～47份、ZrO2的重量份数为2～5份、MnCO3的重量份数为0.2～1份和CaTiO3的重量份数为6～10份。但该文献的制备方法中预烧温度较高，并需额外合成CaTiO3。
US8696925B2公开了一种高介电常数石榴石铁氧体，化学式为Y2.15-2xBi0.5Ca0.35+ 2xZr0.35VxFe4.65-xO12和Bi0.9Ca0.9+2xY1.2-2xZr0.7Nb0.1VxFe4.2-xO12，其x范围分别为0～0.8和0～0.6，该文献的原料中含有带有毒性的V2O5、且预烧温度较高，生产工序复杂且对环境以及人体健康有着不利的影响。
5G通信是未来信息基础设施的重要组成部分，该技术需采用微波作为传输手段，环形器、隔离器作为不可缺少的器件，其小型化、轻量化的任务尤为重要。
如何使用一种介电常数高、△H小、Tc高以及合适的4πMs的微波铁氧体材料使得环形器隔离器小型化、集成化，是目前需要解决的一项技术问题。
发明内容
针对现有技术存在的不足，本发明的目的在于提供一种铁氧体材料及其制备方法和用途。所述铁氧体材料中的Bi和Ca元素能够替代部分稀土Y元素，Zr、W元素能够替代部分Fe离子，利用它们的电磁特性和补偿点来获得合适的4πMs、ΔH和Tc等参数，其中非磁性离子Bi3+对YIG十二面体位Y3+离子的取代，大大提高了材料的介电常数，同时会降低居里温度，而本发明合适的Bi含量可以平衡介电常数与居里温度。对应制备工艺稳定且可重复性好，适合大批量生产，大大降低了生产成本。
为达此目的，本发明采用以下技术方案：
第一方面，本发明提供一种铁氧体材料，所述铁氧体材料的化学式为Bi1.3Cax+ 2yY1.7-x-2yFe5-x-yZrxWyO12；所述x为0.3～0.4，所述y为0.01～1。
例如，所述x可以为0.3、0.32、0.34、0.35、0.38或0.4等；所述y可以为0.01、0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8或1等。
本发明中，所述铁氧体材料中的Bi和Ca元素能够替代部分稀土Y元素，Zr、W元素能够替代部分Fe离子，利用它们的电磁特性和补偿点来获得合适的4πMs、ΔH和Tc等参数，其中非磁性离子Bi3+对YIG十二面体位Y3+离子的取代，大大提高了材料的介电常数，同时会降低居里温度。
优选地，所述铁氧体材料的制备原料包括Bi2O3、CaCO3、Y2O3、Fe2O3、ZrO2和WO3。
优选地，所述Bi2O3、CaCO3、Y2O3、Fe2O3、ZrO2和WO3以如前化学式Bi1.3Cax+2yY1.7-x- 2yFe5-x-yZrxWyO12的化学计量比进行配比。
优选地，所述铁氧体材料中Bi含量为33～33.4wt％，例如33wt％、33.1wt％、33.2wt％、33.3wt％或33.4wt％等。
本发明中，所述铁氧体材料中Bi含量控制在33～33.4wt％，可以实现其介电常数在27.7左右，同时可以平衡介电常数与居里温度。
第二方面，本发明提供一种如第一方面所述的铁氧体材料的制备方法，所述制备方法包括以下步骤：
(1)将铁氧体材料的原料进行混合，烧结，得到铁氧体材料的前驱体；
(2)将步骤(1)所述的铁氧体材料的前驱体再次进行混合，烘干，成型，烧结，得到所述铁氧体材料。
本发明中所提供的制备方法，制备过程稳定且可重复性好，制备得到的铁氧体材料，有着较高的介电常数和居里温度，适合大批量生产，大大降低了生产成本。
优选地，步骤(1)所述混合的方法包括球磨。
优选地，所述球磨包括将所述铁氧体材料的原料、溶剂和磨球放入球磨罐中进行球磨。
优选地，所述溶剂包括水和/或有机溶剂。
优选地，所述有机溶剂包括酒精和/或丙酮，进一步优选为酒精。
本发明中，进一步优选为酒精的原因为酒精为有机溶剂，具有分散效果好，能促进球磨的球磨效率，减少对材料的影响。
优选地，所述磨球包括氧化锆磨球。
优选地，所述球磨的转速为50～100r/min，例如50r/min、60r/min、70r/min、80r/min、90r/min或100r/min等。
优选地，所述球磨的时间为10～20h，例如10h、11h、12h、13h、14h、15h、16h、17h、18h、19h或20h等。
优选地，步骤(1)所述烧结前先进行烘干操作。
优选地，所述烘干的温度为100～200℃，例如100℃、110℃、120℃、130℃、140℃、150℃、160℃、170℃、180℃、190℃或200℃等。
优选地，所述烘干的时间为10～20h，例如10h、11h、12h、13h、14h、15h、16h、17h、18h、19h或20h等。
优选地，步骤(1)所述烧结的升温速率为1～3℃/min，例如1℃/min、1.5℃/min、2℃/min、2.5℃/min或3℃/min等。
优选地，步骤(1)所述烧结的温度为790～830℃，例如790℃、800℃、810℃、820℃或830℃等。
优选地，所述烧结的时间为4～10h，例如4h、5h、6h、7h、8h、9h或10h等。
优选地，步骤(2)所述混合的方法包括球磨。
优选地，所述球磨包括将所述铁氧体材料的前驱体、溶剂和磨球放入球磨罐中进行球磨；
优选地，所述溶剂包括水和/或有机溶剂。
优选地，所述有机溶剂包括酒精和/或丙酮。
优选地，所述磨球包括氧化锆磨球。
优选地，所述球磨的转速为50～100r/min，例如50r/min、60r/min、70r/min、80r/min、90r/min或100r/min等。
优选地，所述球磨的时间为30～40h，例如30h、32h、34h、35h、38h或40h等。
优选地，步骤(2)所述烘干的温度为100～200℃，例如100℃、110℃、120℃、130℃、140℃、150℃、160℃、170℃、180℃、190℃或200℃等。
优选地，所述烘干的时间为10～20h，例如10h、11h、12h、13h、14h、15h、16h、17h、18h、19h或20h等。
优选地，在烘干后的粉料中加入聚乙烯醇溶液。
本发明中，聚乙烯醇起到粘结剂的作用，可以使得烘干后的粉料颗粒之间接触更紧密，利于后续的成型。
优选地，以烘干后的粉料为100％计，所述聚乙烯醇溶液的加入量为0.8～1.5％，例如0.8％、1％、1.2％或1.5％等。
优选地，步骤(2)所述成型的方法包括压制成型。
优选地，所述成型后的物质的成型密度为3.5～3.6g/cm3，例如3.5g/cm3、3.52g/cm3、3.55g/cm3、3.58g/cm3或等3.6g/cm3。
步骤(2)所述烧结包括三次升温操作，所述升温操作包括一次升温、二次升温和三次升温。
本发明中，成型后的烧结过程进行三次升温操作的原因为第一次升温主要是把毛坯内的水份蒸发和粘合剂的挥发过程，需缓缓升温，以避免水份和粘合剂的急剧挥发引起坯件开裂。第二段升温主要是毛坯逐渐收缩,坯件颗粒间发生固相反应,形成晶粒，此时升温速度可快些，第三段升温主要是了抑制Bi2O3的挥发，加快Bi离子的取代。
优选地，所述升温操作的升温速率为1.5～3.5℃/min，例如1.5℃/min、2℃/min、2.5℃/min、3℃/min或3.5℃/min等。
优选地，所述一次升温升至的温度为450～550℃，例如450℃、480℃、500℃、520℃或550℃等。
优选地，所述二次升温升至的温度为750～850℃，例如750℃、760℃、770℃、800℃、820℃、840℃或850℃等。
优选地，所述三次升温升至的温度为1020～1080℃，例如1020℃、1040℃、1050℃、1070℃或1080℃等。
优选地，所述升温后烧结的时间为6～10h，例如6h、7h、8h、9h或10h等。
作为优选的技术方案，本发明中，所述铁氧体材料的制备方法包括以下步骤：
(1)将铁氧体材料的原料、酒精和氧化锆磨球加入球磨罐中，以50～100r/min的球磨速率球磨10～20h，在烘箱中以100～200℃的烘干温度烘干10～20h，烘干后以790～830℃的烧结温度烧结4～10h，得到铁氧体材料的前驱体；
(2)将步骤(1)所述铁氧体材料的前驱体、酒精和氧化锆磨球加入球磨罐中，以50～100r/min的球磨速率球磨30～40h，在烘箱中以100～200℃的烘干温度烘干10～20h，烘干后加入聚乙烯醇溶液，进行压制成型，得到成型密度为3.5～3.6g/cm3的物质，将所述成型后的物质以1.5～3.5℃/min的升温速率升温至450～550℃，再以1.5～3.5℃/min的升温速率升温750～850℃，最后以1.5～3.5℃/min得升温速率继续升温至1020～1080℃的烧结温度烧结6～10h，得到铁氧体材料。
第三方面，本发明还提供一种如第一方面所述的铁氧体材料的用途，所述用途包括将所述铁氧体材料用于微波通信和/或作为磁性材料。
与现有技术相比，本发明具有以下有益效果：
(1)本发明提供的铁氧体材料，其中的Bi、Ca元素能够替代部分稀土Y元素，Zr、W元素能够替代部分Fe离子，利用上述元素的电磁特性和补偿点来获得合适的4πMs、ΔH和Tc，尤其是该铁氧体材料的组配方将Bi含量控制在33～33.4wt％，实现了介电常数为27.7左右，其中非磁性离子Bi3+对YIG十二面体位Y3+离子的取代，大大提高了材料的介电常数，同时会降低居里温度，而本发明合适的Bi含量可以平衡介电常数与居里温度。因此本发明所提供的铁氧体材料的4πMs＝1850±50(Gs)的介电常数在28±2，△H＜60(oe)，居里温度＞240℃，密度＞5.9g/cm3。
(2)本发明提供的制备方法，制备工艺稳定且可重复性好，适合大批量生产，大大降低了生产成本。
具体实施方式
下面通过具体实施例来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
实施例1
本实施例提供一种铁氧体材料，所述铁氧体材料的化学式为(Bi1.3Ca0.5Y1.2Fe4.6Zr0.3W0.1O12)所述铁氧体材料的原料包括纯度为99.95％的Y2O3，纯度为99.95％的Bi2O3，纯度为99％的CaCO3，纯度为99.2％ZrO2，纯度为99.5％的Fe2O3，和纯度为99.5％的WO3。
其制备方法包括以下步骤：
(1)将按照上述化学式配比的铁氧体材料的原料、酒精和氧化锆磨球按照1000:1000:4000的重量配比加入球磨罐中，以60r/min的球磨转速球磨15小时，将球磨后的浆料放入烘箱中以120℃的烘干温度烘干16h，将烘干后的粉料过60目筛放进空气烧结炉进行预烧，以1.5℃/min的速度升温到最高预烧温度830℃，烧结6小时，得到铁氧体材料的前驱体；
(2)将步骤(1)所述铁氧体材料的前驱体、酒精和氧化锆磨球按照1000:1000:5000的重量配比为加入球磨罐中，以60r/min的球磨速率球磨32h，在烘箱中以120℃的烘干温度烘干16h，烘干后加入聚乙烯醇溶液，加入量为所述烘干粉料的质量的1.3％，用100T压机成型进行压制成型，得到成型密度为3.5g/cm3的物质，将所述成型后的物质以2℃/min的升温速率升温至500℃，再以1.66℃/min的升温速率升温至800℃，再以3℃/min继续升温至1020℃的烧结温度烧结10h，经过打磨加工，得到铁氧体材料。
实施例2
本实施例提供一种铁氧体材料，所述铁氧体材料的化学式为Bi1.3Ca0.5Y1.2Fe4.55Zr0.4W0.05O12。所述铁氧体材料的原料包括纯度为99.95％的Y2O3，纯度为99.95％的Bi2O3，纯度为99％的CaCO3，纯度为99.2％ZrO2，纯度为99.5％的Fe2O3，和纯度为99.5％的WO3。
其制备方法包括以下步骤：
(1)将按照上述化学式配比的铁氧体材料的原料、酒精和氧化锆磨球按照1000:1000:4000的重量配比加入球磨罐中，以100r/min的球磨转速球磨10小时，将球磨后的浆料放入烘箱中以180℃的烘干温度烘干12h，将烘干后的粉料过60目筛放进空气烧结炉进行预烧，以2℃/min的速度升温到最高预烧温度810℃，烧结10小时，得到铁氧体材料的前驱体；
(2)将步骤(1)所述铁氧体材料的前驱体、酒精和氧化锆磨球按照1000:1000:5000的重量配比为加入球磨罐中，以80r/min的球磨速率球磨35h，在烘箱中以150℃的烘干温度烘干15h，烘干后加入聚乙烯醇溶液，加入量为所述烘干粉料的质量的0.8％，用100T压机成型进行压制成型，得到成型密度为3.6g/cm3的物质，再将所述物质从室温以2℃/min的升温速率升温至500℃，再以1.66℃/min速率升温至800℃，最后以3℃/min继续升温至1050℃的烧结温度烧结8h，经过打磨加工，得到铁氧体材料。
实施例3
本实施例提供一种铁氧体材料，所述铁氧体材料的化学式为Bi1.3Ca0.4Y1.3Fe4.65Zr0.3W0.05O12。所述铁氧体材料的原料包括纯度为99.95％的Y2O3，纯度为99.95％的Bi2O3，纯度为99％的CaCO3，纯度为99.2％ZrO2，纯度为99.5％的Fe2O3，和纯度为99.5％的WO3。
其制备方法包括以下步骤：
(1)将按照上述化学式配比的铁氧体材料的原料、酒精和氧化锆磨球按照1000:1000:4000的重量配比加入球磨罐中，以100r/min的球磨转速球磨10小时，将球磨后的浆料放入烘箱中以180℃的烘干温度烘干12h，将烘干后的粉料过60目筛放进空气烧结炉进行预烧，以1.5℃/min的速度升温到最高预烧温度790℃，烧结6小时，得到铁氧体材料的前驱体；
(2)将步骤(1)所述铁氧体材料的前驱体、酒精和氧化锆磨球按照1000:1000:5000的重量配比为加入球磨罐中，以80r/min的球磨速率球磨35h，在烘箱中以150℃的烘干温度烘干15h，烘干后加入聚乙烯醇溶液，加入量为所述烘干粉料的质量的1％，用100T压机成型进行压制成型，得到成型密度为3.55g/cm3的物质，再将所述物质从室温以2℃/min的升温速率升温至500℃，再以1.66℃/min速率升温至800℃，最后以3℃/min继续升温至1080℃的烧结温度烧结6h，经过打磨加工，得到铁氧体材料。
实施例4
本实施例与实施例1区别为，步骤(2)中升温后的烧结温度为1000℃，其余制备方法与参数与实施例1保持一致。
实施例5
本实施例与实施例1区别为，步骤(2)中升温后的烧结温度为1100℃。
其余制备方法与参数与实施例1保持一致。
实施例6
本实施例与实施例1的区别为本实施例步骤(2)中升温后的烧结时间为25h。
其余制备方法与参数与实施例1保持一致。
实施例7
本实施例与实施例1的区别为本实施例步骤(2)中升温后的烧结时间为3h。
其余制备方法与参数与实施例1保持一致。
对比例1
本对比例提供一种铁氧体材料，所述铁氧体材料的化学式为Bi1.3Ca0.3Y1.4Fe4.7Zr0.3O12。所述铁氧体材料的原料包括纯度为99.95％的Y2O3，纯度为99.95％的Bi2O3，纯度为99％的CaCO3，纯度为99.2％ZrO2，纯度为99.5％的Fe2O3。
其制备方法包括以下步骤：
(1)将按照上述化学式配比的铁氧体材料的原料、酒精和氧化锆磨球按照1000:1000:4000的重量配比加入球磨罐中，以60r/min的球磨转速球磨15小时，将球磨后的浆料放入烘箱中以120℃的烘干温度烘干16h，将烘干后的粉料过60目筛放进空气烧结炉进行预烧，以1.5℃/min的速度升温到最高预烧温度830℃，烧结6小时，得到铁氧体材料的前驱体；
(2)将步骤(1)所述铁氧体材料的前驱体、酒精和氧化锆磨球按照1000:1000:5000的重量配比为加入球磨罐中，以60r/min的球磨速率球磨32h，在烘箱中以120℃的烘干温度烘干16h，烘干后加入聚乙烯醇溶液，加入量为所述烘干粉料的质量的1.3％，用100T压机成型进行压制成型，得到成型密度为3.5g/cm3的物质，将所述成型后的物质以2℃/min的升温速率升温至500℃，再以1.66℃/min的升温速率升温至800℃，再以3℃/min继续升温至1020℃的烧结温度烧结10h，经过打磨加工，得到铁氧体材料。
对比例2
本对比例提供一种铁氧体材料，所述铁氧体材料的化学式为Bi1.3Ca0.9Y1.0Fe4.4Zr0.5W0.1O12。所述铁氧体材料的原料包括纯度为99.95％的Y2O3，纯度为99.95％的Bi2O3，纯度为99％的CaCO3，纯度为99.2％ZrO2，纯度为99.5％的Fe2O3，和纯度为99.5％的WO3。
其制备方法包括以下步骤：
(1)将按照上述化学式配比的铁氧体材料的原料、酒精和氧化锆磨球按照1000:1000:4000的重量配比加入球磨罐中，以60r/min的球磨转速球磨15小时，将球磨后的浆料放入烘箱中以120℃的烘干温度烘干16h，将烘干后的粉料过60目筛放进空气烧结炉进行预烧，以1.5℃/min的速度升温到最高预烧温度830℃，烧结6小时，得到铁氧体材料的前驱体；
(2)将步骤(1)所述铁氧体材料的前驱体、酒精和氧化锆磨球按照1000:1000:5000的重量配比为加入球磨罐中，以60r/min的球磨速率球磨32h，在烘箱中以120℃的烘干温度烘干16h，烘干后加入聚乙烯醇溶液，加入量为所述烘干粉料的质量的1.3％，用100T压机成型进行压制成型，得到成型密度为3.5g/cm3的物质，将所述成型后的物质以2℃/min的升温速率升温至500℃，再以1.66℃/min的升温速率升温至800℃，再以3℃/min继续升温至1020℃的烧结温度烧结10h，经过打磨加工，得到铁氧体材料。
用排水法测试实施例1-7与对比例1-2制备得到的铁氧体材料的密度。
将实施例1-7与对比例1-2制备得到的铁氧体材料加工成Φ1.6×22的细棒测试其介电常数ε。
将实施例1-7与对比例1-2制备得到的铁氧体材料抛光成Φ1圆球测试△H。
将实施例1-7与对比例1-2制备得到的铁氧体材料加工成Φ2.5mm圆球测试4πMs和居里温度Tc。
表1为对实施例1-7与对比例1-2制备得到的铁氧体材料进行上述测试后的结果汇总。
表1
Figure BDA0002758783180000121
Figure BDA0002758783180000131
从以上所述的具体实施例及对比例数据分析，不同W2O3及ZrO2比例及烧结温度及保温时间对材料的4πMs、线宽及烧结密度有很大的影响。
从实施例1与实施例4-5的数据结果可知，烧结过程中温度过低，晶粒没有长大，密度低，导致线宽高；烧结温度过高会导致氧化铋的析出，也会使得密度降低，线宽恶化。
从实施例1与实施例6-7的数据结果可知，烧结过程中烧结时间过长，容易导致氧化铋的析出，造成密度低，线宽恶化；烧结时间过短会导致晶粒长不大，仍会造成密度低，线宽高。
从实施例1与对比例1的数据结果可知，铁氧体材料中不含W元素时，其结果会线宽偏高。
从实施例1与对比例2的数据结果可知，铁氧体材料中Zr元素含量过多时会导致4πMS降低，线宽恶化。
综上可以看出，本发明中所提供的铁氧体材料，其可以更好地平衡介电常数与居里温度，并具有线宽小、Tc高以及合适的4πMs的特点，能够更好地应用于微波通信或作为磁性材料。
以上所述的具体实施例，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施例而已，并不用于限制本发明，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (40)

1.一种铁氧体材料，其特征在于，所述铁氧体材料的化学式为Bi1.3Cax+2yY1.7-x-2yFe5-x- yZrxWyO12；所述x为0.3～0.4，所述y为0.01～1，所述铁氧体材料中Bi含量为33～33.4wt％。
2.根据权利要求1所述的铁氧体材料，其特征在于，所述铁氧体材料的制备原料包括Bi2O3、CaCO3、Y2O3、Fe2O3、ZrO2和WO3。
3.根据权利要求2所述的铁氧体材料，其特征在于，所述Bi2O3、CaCO3、Y2O3、Fe2O3、ZrO2和WO3以化学式Bi1.3Cax+2yY1.7-x-2yFe5-x-yZrxWyO12的化学计量比进行配比。
4.根据权利要求1-3任一项所述的铁氧体材料的制备方法，其特征在于，所述制备方法包括以下步骤：
(1)将铁氧体材料的原料进行混合，烧结，得到铁氧体材料的前驱体；
(2)将步骤(1)所述的铁氧体材料的前驱体再次进行混合，烘干，成型，烧结，得到所述铁氧体材料。
5.根据权利要求4所述的铁氧体材料的制备方法，其特征在于，步骤(1)所述混合的方法包括球磨。
6.根据权利要求5所述的铁氧体材料的制备方法，其特征在于，所述球磨包括将所述铁氧体材料的原料、溶剂和磨球放入球磨罐中进行球磨。
7.根据权利要求6所述的铁氧体材料的制备方法，其特征在于，所述溶剂包括水和/或有机溶剂。
8.根据权利要求7所述的铁氧体材料的制备方法，其特征在于，所述有机溶剂包括酒精和/或丙酮。
9.根据权利要求8所述的铁氧体材料的制备方法，其特征在于，所述有机溶剂为酒精。
10.根据权利要求6所述的铁氧体材料的制备方法，其特征在于，所述磨球包括氧化锆磨球。
11.根据权利要求5所述的铁氧体材料的制备方法，其特征在于，所述球磨的转速为50～100r/min。
12.根据权利要求5所述的铁氧体材料的制备方法，其特征在于，所述球磨的时间为10～20h。
13.根据权利要求4所述的铁氧体材料的制备方法，其特征在于，步骤(1)所述烧结前先进行烘干操作。
14.根据权利要求13所述的铁氧体材料的制备方法，其特征在于，所述烘干的温度为100～200℃。
15.根据权利要求13所述的铁氧体材料的制备方法，其特征在于，所述烘干的时间为10～20h。
16.根据权利要求4所述的铁氧体材料的制备方法，其特征在于，步骤(1)所述烧结的升温速率为1～3℃/min。
17.根据权利要求4所述的铁氧体材料的制备方法，其特征在于，步骤(1)所述烧结的温度为790～830℃。
18.根据权利要求4所述的铁氧体材料的制备方法，其特征在于，所述烧结的时间为4～10h。
19.根据权利要求4所述的铁氧体材料的制备方法，其特征在于，步骤(2)所述混合的方法包括球磨。
20.根据权利要求19所述的铁氧体材料的制备方法，其特征在于，所述球磨包括将所述铁氧体材料的前驱体、溶剂和磨球放入球磨罐中进行球磨。
21.根据权利要求20所述的铁氧体材料的制备方法，其特征在于，所述溶剂包括水和/或有机溶剂。
22.根据权利要求21所述的铁氧体材料的制备方法，其特征在于，所述有机溶剂包括酒精和/或丙酮。
23.根据权利要求22所述的铁氧体材料的制备方法，其特征在于，所述有机溶剂为酒精。
24.根据权利要求20所述的铁氧体材料的制备方法，其特征在于，所述磨球包括氧化锆磨球。
25.根据权利要求19所述的铁氧体材料的制备方法，其特征在于，所述球磨的转速为50～100r/min。
26.根据权利要求19所述的铁氧体材料的制备方法，其特征在于，所述球磨的时间为30～40h。
27.根据权利要求4所述的铁氧体材料的制备方法，其特征在于，步骤(2)所述烘干的温度为100～200℃。
28.根据权利要求4所述的铁氧体材料的制备方法，其特征在于，所述烘干的时间为10～20h。
29.根据权利要求4所述的铁氧体材料的制备方法，其特征在于，在烘干后的粉料中加入聚乙烯醇溶液。
30.根据权利要求29所述的铁氧体材料的制备方法，其特征在于，以烘干后的粉料为100％计，所述聚乙烯醇溶液的加入量为0.8～1.5％。
31.根据权利要求4所述的铁氧体材料的制备方法，其特征在于，步骤(2)所述成型的方法包括压制成型。
32.根据权利要求4所述的铁氧体材料的制备方法，其特征在于，所述成型后的物质的成型密度为3.5～3.6g/cm3。
33.根据权利要求4所述的铁氧体材料的制备方法，其特征在于，步骤(2)所述烧结包括三次升温操作，所述升温操作包括一次升温、二次升温和三次升温。
34.根据权利要求33所述的铁氧体材料的制备方法，其特征在于，所述升温操作的升温速率为1.5～3.5℃/min。
35.根据权利要求33所述的铁氧体材料的制备方法，其特征在于，所述一次升温升至的温度为450～550℃。
36.根据权利要求33所述的铁氧体材料的制备方法，其特征在于，所述二次升温升至的温度为750～850℃。
37.根据权利要求33所述的铁氧体材料的制备方法，其特征在于，所述三次升温升至的温度为1020～1080℃。
38.根据权利要求33所述的铁氧体材料的制备方法，其特征在于，所述升温后烧结的时间为6～10h。
39.根据权利要求4所述的铁氧体材料的制备方法，其特征在于，所述制备方法包括以下步骤：
(1)将铁氧体材料的原料、酒精和氧化锆磨球加入球磨罐中，以50～100r/min的球磨速率球磨10～20h，在烘箱中以100～200℃的烘干温度烘干10～20h，烘干后以790～830℃的烧结温度烧结4～10h，得到铁氧体材料的前驱体；
(2)将步骤(1)所述铁氧体材料的前驱体、酒精和氧化锆磨球加入球磨罐中，以50～100r/min的球磨速率球磨30～40h，在烘箱中以100～200℃的烘干温度烘干10～20h，烘干后加入聚乙烯醇溶液，进行压制成型，得到成型密度为3.5～3.6g/cm3的物质，将所述成型后的物质以1.5～3.5℃/min的升温速率升温至450～550℃，再以1.5～3.5℃/min的升温速率升温750～850℃，最后以1.5～3.5℃/min得升温速率继续升温至1020～1080℃的烧结温度烧结6～10h，得到铁氧体材料。
40.一种如权利要求1-3任一项所述的铁氧体材料的用途，其特征在于，所述用途包括将所述铁氧体材料用于微波通信和/或作为磁性材料。
CN202011211159.XA 2020-11-03 2020-11-03 一种铁氧体材料及其制备方法和用途 Active CN112358290B (zh)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN202011211159.XA CN112358290B (zh) 2020-11-03 2020-11-03 一种铁氧体材料及其制备方法和用途
PCT/CN2021/075239 WO2022095296A1 (zh) 2020-11-03 2021-02-04 一种铁氧体材料及其制备方法和用途
EP21888001.1A EP4119523A4 (en) 2020-11-03 2021-02-04 FERRITE MATERIAL, PREPARATION METHOD AND USE THEREOF

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011211159.XA CN112358290B (zh) 2020-11-03 2020-11-03 一种铁氧体材料及其制备方法和用途

Publications (2)

Publication Number Publication Date
CN112358290A CN112358290A (zh) 2021-02-12
CN112358290B true CN112358290B (zh) 2022-05-13

Family

ID=74512721

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011211159.XA Active CN112358290B (zh) 2020-11-03 2020-11-03 一种铁氧体材料及其制备方法和用途

Country Status (3)

Country Link
EP (1) EP4119523A4 (zh)
CN (1) CN112358290B (zh)
WO (1) WO2022095296A1 (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114956800B (zh) * 2022-05-23 2023-07-07 西南应用磁学研究所(中国电子科技集团公司第九研究所) 一种高性能微波多晶铁氧体材料
CN115340371B (zh) * 2022-07-26 2023-07-21 深圳顺络电子股份有限公司 一种铁氧体材料、制备方法及微波通信器件
CN115331907B (zh) * 2022-09-01 2023-11-21 南京金宁微波有限公司 一种应用于大功率微波器件的旋磁铁氧体材料及其制备方法

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4987514B2 (ja) * 2007-03-08 2012-07-25 株式会社東芝 磁気冷凍材料、及び磁気冷凍装置
US8696925B2 (en) * 2010-11-30 2014-04-15 Skyworks Solutions, Inc. Effective substitutions for rare earth metals in compositions and materials for electronic applications
US9527776B2 (en) * 2010-11-30 2016-12-27 Skyworks Solutions, Inc. Effective substitutions for rare earth metals in compositions and materials for electronic applications
KR101945829B1 (ko) * 2011-06-06 2019-02-11 스카이워크스 솔루션즈, 인코포레이티드 희토류 감소된 가닛계 및 관련 마이크로파 애플리케이션
CN102976729A (zh) * 2012-11-14 2013-03-20 东阳富仕特磁业有限公司 一种窄线宽高介电常数石榴石微波铁氧体
US9552917B2 (en) * 2013-09-20 2017-01-24 Skyworks Solutions, Inc. Materials, devices and methods related to below-resonance radio-frequency circulators and isolators
US10181632B2 (en) * 2013-12-18 2019-01-15 Skyworks Solutions, Inc. Tunable resonators using high dielectric constant ferrite rods
US9771304B2 (en) * 2015-06-15 2017-09-26 Skyworks Solutions, Inc. Ultra-high dielectric constant garnet
CN105174934A (zh) * 2015-08-31 2015-12-23 天长市中德电子有限公司 一种高饱和磁感应强度宽温低损耗软磁铁氧体的制备方法
WO2017200091A1 (ja) * 2016-05-20 2017-11-23 Tdk株式会社 フェライト磁石
CN109563640B (zh) * 2016-07-13 2021-11-05 天工方案公司 温度不敏感介电常数石榴石
CN107746269B (zh) 2017-10-31 2020-12-04 深圳市华扬通信技术有限公司 低损耗功率旋磁材料及其制备方法
CN111285673A (zh) * 2020-02-13 2020-06-16 深圳顺络电子股份有限公司 一种高介电常数微波铁氧体材料、制备方法及微波通信器件
CN111848149B (zh) * 2020-07-09 2022-12-30 深圳顺络电子股份有限公司 一种高介电常数微波铁氧体材料、制备方法和器件

Also Published As

Publication number Publication date
CN112358290A (zh) 2021-02-12
EP4119523A1 (en) 2023-01-18
WO2022095296A1 (zh) 2022-05-12
EP4119523A4 (en) 2024-04-24

Similar Documents

Publication Publication Date Title
CN112358290B (zh) 一种铁氧体材料及其制备方法和用途
CN112679204B (zh) 一种高饱和高介电常数低线宽微波铁氧体材料及其制备方法
CN111848149B (zh) 一种高介电常数微波铁氧体材料、制备方法和器件
CN111116192B (zh) 一种微波铁氧体材料、制备方法及微波通信器件
CN112194483B (zh) 一种高强度钙镁钛系微波介质陶瓷材料及其制备方法
CN114477995B (zh) 一种中饱和磁化强度功率型高介电常数石榴石材料及其制备方法
CN112679207A (zh) 一种永磁铁氧体材料及其制备方法
CN110372365A (zh) 一种永磁铁氧体材料的制备方法
KR20170142776A (ko) 페라이트 자성재료 및 페라이트 소결자석
CN113651609A (zh) 一种微波铁氧体材料及其制备方法与应用
CN111302787A (zh) 一种具有高Qf高强度的微波介质陶瓷材料及其制备方法
CN111116193B (zh) 一种微波铁氧体材料及其制备方法和器件
CN112592170A (zh) 锰锌铁氧体材料及其制备方法和应用
CN112159218A (zh) 一种低成本高性能永磁铁氧体材料的制备方法
CN113896521B (zh) 一种低饱和窄线宽旋磁材料及其制备方法
CN112898008A (zh) 一种低损耗yig铁氧体及其制备方法
CN111925201A (zh) Sc掺杂六角晶系Zn2W铁氧体材料及制备方法
KR20150048256A (ko) 자성 분말, 그 제조 방법, 및 이를 포함하는 자석
CN112390637A (zh) 无钇配方的高介电常数微波铁氧体材料及其制备方法和器件
CN112851325A (zh) 高饱和磁化强度z型六角铁氧体粉末及其制备方法
CN115259849B (zh) 旋磁铁氧体材料及制备方法和应用
CN112939595B (zh) 高温下近零温度系数的微波介质陶瓷材料及其制备方法
CN114436635B (zh) 具有高自旋波线宽的微波铁氧体材料及其制备方法
CN111943659A (zh) 一种高频低损耗高电阻率镍锌铁氧体材料的制备工艺
CN112645702A (zh) 一种宽频宽温高磁导率Mn-Zn铁氧体材料及其制备方法与应用

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant